Process of dyeing textile fibers



Patented Apr 7, 1931 UNITED STATES JEAN GEORGES OF WALTHAM, MASSAGHUSE'I'TS, CHARLES J. GALA, 03

PATENT OFFICE WILMINGTON, DELAWARE, ASSIGNORS 'I'O E. 1. DE POINT DE NEIOURS 6'6 (DKPANY,

OF WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE PROCESS OF'DYEINGTEZTILE FIBERS lio Drawing. Original application tilled. August 4, 1927, Serial No. 216,714. Dividedand this application filed March 21, 1930.

This case'is adivision of our copending application Serial-No. 210,714, filed August This invention relates to alkylolamine salts of aliphatic acids both saturated and unsaturated and to the sulfonic acid derivatives of these acids and more particularly to the ethanolamine salts of the higher fatty acids.

. This invention has as objects the preparation of soluble oils, solvents and detergents as well as of antiseptic soaps. These objects are accomplished by making thesalts of the bases known as alkylolamines or hydroxy-alkylamines, more particularly of the ethanolamine's, by combination with the fatty acids mentioned above by any of the will known methods for the production of sa ts.

The bases used for our purpose ma be represented by the following general ormula:

where Alk represents an ali hatic or hydroxy aliphatic radical, R and 2 represent hydrogen or an aliphatic radical or a hydroxy aliphatic radical or a poly hydroxy aliphatic radical. In making these new 'soluble oils we may proceed as follows: I

The free fatty acids are combined directl ly with an organic base or a mixture of suc bases. If the fatty acid is asolid the reparation is aided-by the application 0 heat.

It is also possible to start from the glycerides of the fatty acids, i. e., olive oil, cottonseed oil, castor oil, linseed oil and the like b saponifying the glycerides by heating wit the base to a high temperature. In th1s case we find that iilzhe reaction is complete when I,

Serial No. 431,940.

from the sulfonated fatty acids we may pro-' ceed as follows:

The acid product of the mixture of the sulfonated unsaturated acid as obtained by the action of sulfuric acid on an unsaturated oil such as castor oil in the well known man-' ner is freed of mineral acid by washing. It is then freed of water either by settling or by any other suitable means and then enough of the alkylolamine base is added at ordinary temperature to neutralize the acidity of the sulfonic acid group or of both sulfonic acid and the carboxylic acid groups. The following examples will serve to illustrate our method of procedure, but it is to be underamine and 20% of di-ethano amine.

The products resulting from this procedure are semi-solids, particularly watzr soluble and ready for use 'without further reatm'ent. It is possible that the resultant material may be a compound of the base with the oleic acid but this has not been definitel established ,and is, in fact, immaterial to t e success of the invention.

- fE'wampleg w a 298.37 m; ofti lnoleic. acid c' on c" n a a a; -3 a xed parts di-ethanolamine.

The resultant product is clear very soluble in water. I

Ewample J; V

372 parts castor oil are mixed with 260 parts tri-ethanolamine 200 parts water.

The above mixture is heated on the water bath for several hours. The saponification proceeds slowly and in order to make it coman... oil,

plete within reasonable time it is of advantage to add an excess, forexample 30% triethanolarn'ine, above the quantity mentioned.

Ewample 5 284. 39 parts 0t stearic acid are melted. Into the melt are stirred 149 parts tri-ethanolamine,-stirring is continued at a Example 6 282 parts oleic acid 91 parts of amino-propane diol are heated together until completely mixed. The product is very soluble in alcohol. In water the solution is cloudy but becomes clear on the addition of some excess base, e. g. 15

Example '7 282 parts oleic acid are caused to react as given in the above example with 119 parts of methyl di-ethanolamine CH3-N= (CH2- ongoing The soap obtained in this way has the property, when 1n alcoholic solution, of dissolving mercur1c oxide and giving a relatively stable product soluble in water. This 18 altogether a surprising result and illustrates the use of these new soaps for pharmaceutical purposes.

Example 8 6 parts of a crude sulfonated oil made b the action of sulfuric acid on castor oil are mixed with 1 part of mono-ethanolamine.

Emample 9 2. 7 parts of a crude sulfonated oil mixture in the form of free acids are mixed with 1 part of a mixture of diand tri-ethanolamine.

The products of examples 8 and 9 are entirely soluble in water. They are thick yellow oils presumably containing salts of the bases of the sulfonic acids but this point has not been definitely established and is immaterial to the success of the invention. The products formed in this way are quite satisfactory for ordinary purposes.

In dyeing Ponsol blue GD double paste, Schultz No. 842, on cotton yarn in the package machine, using 5% of color, 2 sodium hydroxide, 3% hydrosulfite, the addition of 1% of the product formed by combining 1 mole of sulfo-ricinoleic acid and 1 mole triethanolamine, containing diethanolamine, results in a brighter, more level dyeing.

The use in dyeing of the new compounds described in this case can be illustrated by the following example:

E trample 10 piece goods is obtained as follows:

' 12.7 5 pounds Ponsol blue GD, Schultz No.

842, are mixed with 8.16 pounds of oneof the compounds described in the examples of this case; 1 gallon of cold water is added and the suspension passed through a fine screen. A perfect speckless paste is thus obtained, which is added to the jigger dye bath composed of the following:

10 pounds caustic soda 15 pounds hydrosulflte concentrated, 10 pounds being added immediately and 5 pounds being added after one passage of the goods. 100 gallons of water.

The temperature is raised to 110 F., and after complete reduction the dyeing started at this temperature. The temperature is then allowed to rise during 30 minutes to 125 0., and further dyed at this temperature for 10 to 15 minutes. Then give 1 wash, 4 passages in sodium perborate, 2 lbs. per 100 gals. at 120 F., 2 cold washes, 5 passes in boiling soap solution 3 lbs. soap to 100 gallons, then rinse and wash in the open, dry and calender.

This example, illustrating the method of dyeing, is similar to Example 1 given in copending application Serial No. 210,715, filed by applicants on August 4, 1927. The difi'erence between this exam le and the said Example 1 lies in the substitution of the novel assistants herein disclosed by applicants.

Ewample 11 The new compounds described in this application ma be used as assistants in the making of vat co or pastes in a manner similar to the pastes described in applicants patented application bearing Patent Number 1,705,118, granted March 19, 1929. The dyestufi' paste, as produced in the course of manufacture of Ponsol blue GD, Schultz No. 842, is converted into a press cake containing 30% of dry color. 400 parts of the press cake are then mixed with,20 parts of glycerine and 580 parts of one of the assistants prepared according to Examples 1 to 9 and Example 13 of this application. It is possible to vary the quantities considerably without losing the advantages of this invention.

E mample 12 The new compounds described in this case may be used in printing pastes containing lakes of basic colors. The mode of procedure in using such a printing paste is illustrated in the following example:

10 parts basic color (suitable for discharge printing) 50 parts gl cerine 50 parts 0 any one o! the products described in Examples 1 to 9 and Example 13 of this application 250 parts water 580 parts thickening composed of starch or gums and a certain amount of sodium hydrosulflte-formaldehyde necessary to cut the ground 60 parits Itlai'min dissolved in equal parts of water or The textile or other material printed with this composit1on is aged and heated, passed into These products for these reasons have a disk 'may be used either alone or in mixture.

solution or dispersion in so mas s}-31: I

Salts, washed. and finished .s'usuaf p";

The process of printin illustrated inthis-example is identical wit Example 4 in appli- May 31, 1927, except for the insertion of the new assistants which comprise part of applicants herein disclosed invention.

. If a pure product is needed the operation may be carried out as follows:

378 parts of pure .sulfo-rlclnoleic acid prepared by the action of chloro-lultonlc acid on pure rlclnoleic acid are mixed with 149 parts of trl-ethanolamine. v

In the above case theaddition of a further molecular equivalent of-base'produces a more soluble oil. The reason may be that the extra quantity of base combines with the carboxyl group but again this point has not been determlned.

In the above examples any one of the bases as defined by the general formula given above The fatty acids may also be varied through a wide range.

By the term alkylol, as used herein, we mean to include an alkyl radical in which one. or more hydrogens are replaced by a hydroxyl p, and y be p e t d by the e l combination of a substance from the group lowing:

o,,H2;,.oH or -O,,H 1(OH) We have found that these products, which are essentially-organic soaps possess a greater dissolving power or dispersin power for organic substances than do-"or 'nary soaps. They possess the detergent property of soaps without the high alkalinity characteristic or sodium or potassium salts of the fatty acids.

tinctadvantage for many urposesand parf ticularly as assistants in yeing, and -fthose" compounds which are derived from 'sulfonated castor oil by the process mentioned are in many ways superior to ordinary sulfonated.

oils. Their superiority is evidenced by the brilliance-of the dyeingfi.

When added to waterthe to appear a solution of insoluble organic bases such as amino-azo-benzene, para nitro- 5 parts of the solvent for 1 part of the insoluble base. These solutions may be used very successfully for the purpose of dyeing fibers of esterified cellulose.

It has also been found that these soaps dis- 7 salve metallic hydroxide and oxides, for ex- .tri-ethanolaminer ii 2 :4. In alprocessof a 1 indicates-rth robab1 valence-in p r aantiseptie soapsjand thelike.

-cology," for example, in the production of cants co-pending case Serial No. 195,579, filed bodiments 0 {thisinventionfmay be made' withoutdepa'rtingfrom the spirit thereof, it

is to be undersi'DQdthat we do not intend to limit ourselves ftoljthe specific embodimentsclaims. j H

1. In a process'oi applyin'g a "dyeto textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of a substance from the group consisting of sulfo -ricinoleic acid, and the product formed 'bf sulphonation of castor thereof except as indicated in the appended I oil, .withanjalkylo amine.

In a process oiapplying a dyeto textile fibers, the stepwhichcomprises mixing with said dye a product" resulting from the chemicalicombination of -a substance from the group consisting of sulfo-ricinoleic acid, and the productforme'd by the sulphonation of castor oil, with an ethanolamine;

j 3. In a process of applyinga dye textile fibers the step which COIDPIISESI mixing with said dye a product-resulting'from the chemiconsistin of -sulfmricinole ic. acid, and the the gro p consisting of di-ethanolamine -and product rmed byf'the sulphonation of castor oil, with a substance taken from the grou diol.

greater evenness of, the shades d lg d the i a h ep Whlch mprises mixing 1; better utilization of the color, and the gr ater.

said yea product resulting from the chemicalpombination ofa substance from the group consistin' of sulfo-ricinoleic acid, and the fbring'a' ut. Be a. Orm as product ormed by the sulphonation of castor oil, with tri-ethanolamine.

6. In a process of applying a dye to textile fibers the step which comprises mixing with said dye a product resulting from the chemical combination of a substance from the group consistin product ormed by the sulphonation of castor oil, with an excess of tri-ethanolamine.

' 7 In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of a substance from the group consistin of sulfo-ricinoleic acid and the product ormed by the sulphonation of castor.

a dye to textile .fibe'stm step which comprises mixing with s n.

of sul'fo-ricinoleic acid, and the yeaproduct resulting from the chemi calcoinbination of. a substance from the group of ;sulfo'-ricinoleic acid, and the o oil, with a compound having the following formula:

/A1kOH N -R| in which All; represents an aliphatic or hydroxy aliphatic radical, while both R and R represent a nionovalent substance from the group consisting of hydrogen, aliphatic radicals, hydroxy aliphatic radicals and polyhy: droxy aliphatic radicals.

8. In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid and the product formed by the sulphonation of castor oil, with a mixture of diand tri-ethanolamines.

9. In a process of applying a dye to textile I fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of a substance from the group consistin of sulfo-ricinoleic acid and the product ormed by the sulphonation of castor oil, with di-ethanolamine. i

10. In a process of applying a dye to textile fibers, the step which comprises mixing so with said dye a product resulting from the chemical combination of a substance from the group consisting of sulfo-ricinoleic acid and the product formed by the sulphonation of castor oil, with mono-ethanolamine.

25 In testimony whereof we aflix our signatures.

JEAN GEORGES KERN. CHARLES J. SALA. 

